Deterioration preventive for concrete or mortar and method for preventing deterioration of concrete or mortar

ABSTRACT

The present invention provides a deterioration inhibitor for concrete or mortar which does not pollute water and which, in a small amount, can prevent the deterioration of concrete or mortar due to sulfur oxidizing bacteria for a long time, and also provides a method of inhibiting the deterioration of concrete or mortar which uses the deterioration inhibitor. A phthalocyanine compound is an effective component of the deterioration inhibitor for concrete or mortar. In the method of inhibiting the deterioration of concrete or mortar, the phthalocyanine compound is added to concrete or mortar.

TECHNICAL FIELD

The present invention relates to a deterioration inhibitor for concreteor mortar which inhibits and/or kills sulfur oxidizing bacteria and to amethod of inhibiting the deterioration of concrete or mortar which usesthe deterioration inhibitor. More particularly, the present inventionrelates to a deterioration inhibitor for concrete or mortar and to amethod of inhibiting the deterioration of concrete or mortar which arepreferably used for concrete or mortar structures in sewerage systems orthe like.

BACKGROUND ART

In recent years, deterioration of concrete structures in seweragesystems or the like in Japan has been reported frequently. Deteriorationoccurs not only in Japan but also in other countries and has beenreported in Australia, Egypt, South Africa, the U.S., and the like.Because it costs a large amount of money to build sewerage systems orthe like, it is important to take appropriate measures against thedeterioration of concrete so as to enable the system effectively tofunction over a long time.

It is known that the deterioration of concrete is caused by two types ofmicroorganisms, i.e., sulfate reducing bacteria and sulfur oxidizingbacteria such as the genus Thiobacillus or the like. In the process ofthe deterioration of concrete by these microorganisms, firstly, sulfatein sewage (normally, the concentration of sulfate in sewage is withinthe range of 20 to 40 mg/l) is reduced by the sulfate reducing bacteriaunder anaerobic conditions and hydrogen sulfide is thereby generated.Next, the hydrogen sulfide is absorbed by water on the concrete wallsurface and is oxidized by sulfur oxidizing bacteria under aerobicconditions. Sulfuric acid is thereby generated. Calcium in the concreteis changed to calcium sulfate (plaster) by the generated sulfuric acid.In this way, the concrete becomes fragile (deteriorates).

Among the aforementioned two types of microorganisms, the sulfuroxidizing bacteria is considered to be the main cause of thedeterioration of concrete. Various methods have been proposed forinhibiting the change of hydrogen sulfide to sulfuric acid by the sulfuroxidizing bacteria.

One of these methods is a method of reducing the concentration ofhydrogen sulfide which is a substrate for sulfur oxidizing bacteria. Forexample, methods are known in which air or oxygen is injected intosewage to oxidize hydrogen sulfide before the hydrogen sulfide isabsorbed by water on the concrete wall surface, and to suppress theactivity of the anaerobic sulfate reducing bacteria so that thegeneration of hydrogen sulfide is reduced. Among these methods, themethod of injecting air into the sewage is a relatively simple method.However, in this method, the injected air may affect the equilibriumbetween the gas and liquid of the hydrogen sulfide such that the amountof hydrogen sulfide diffused in the air is larger than that in a case inwhich air is not injected. Further, hydrogen sulfide can be oxidizedmore effectively in the method of injecting oxygen into the sewage thanin the method of injecting air. However, there is a drawback in that thecost of the method is high.

Another inhibiting method is a method of adding a large amount ofchlorine, hydrogen peroxide, potassium permanganate, or a metallic saltwhose metal is iron, zinc, lead, copper, or the like into sewage so thatthe hydrogen sulfide within the sewage bonds therewith. Further,Japanese Patent Application Laid-Open (JP-A) No. 7-70561 discloses amethod of inhibiting the deterioration of concrete in which awater-soluble quinone derivative is added into sewage to oxidizehydrogen sulfide and to suppress the activity of the anaerobic sulfatereducing bacteria. However, since the material added into the sewagedisappears as it flows, these methods are not effective and areexpensive.

Moreover, a method of inhibiting the deterioration of concrete is knownin which sulfur oxidizing bacteria is killed by mixing an antibacterialagent, which is an organic compound, with concrete. However, theantibacterial agent may generate pinholes or cracks in the concrete andmay reduce the durability of the concrete. Further, at present, the useof Na--PCP (sodium pentachlorophenol) having a strong antibacterialaction is prohibited.

Further, it is known that the growth of sulfur oxidizing bacteria isinhibited by a metal ion. JP-A No. 4-149053 discloses a method ofinhibiting the deterioration of concrete in which a metal (e.g., copper,nickel, tin, lead or the like which is difficult to dissolve in waterand is soluble in sulfuric acid) or the oxide of such a metal is addedto concrete. In this method, metal ion is eluted from the metal and/orthe metal oxide by sulfuric acid generated by sulfur oxidizing bacteriaand inhibits and/or kills the sulfur oxidizing bacteria. However, inthis method, because a metal having high solubility in sulfuric acid, ora metallic oxide having high solubility in sulfuric acid, or a mixturethereof is used, in order to prevent the deterioration of concrete overa long time, a large amount of metal or the like must be used. Further,since the heavy metal ion of nickel, tin, lead or the like is elutedinto the sewage, water pollution may be caused by these metals.

Furthermore, JP-A No. 6-16460 and JP-A No. 6-16461 disclose methods ofinhibiting the deterioration of concrete in which a metal complex suchas nickelocene or nickeldimethylglyoxime is added to concrete. However,these metal complexes are carcinogenic and cause problems in terms ofsafety.

Several methods which use a material having resistance to sulfuric acidhave also been proposed as methods of inhibiting the deterioration ofconcrete. For example, JP-A No. 63-16072 and JP-A No. 2-265708 disclosemethods of protecting concrete by the lining of an epoxy resin, apolyester resin, or the like. Moreover, JP-A No. 1-55493 discloses amethod of protecting concrete by the lining of a glass material.

However, in these methods, the construction cost is high, and since thelined material is peeled through pinholes, the life of concrete isshort. Therefore, in order to maintain the effect of inhibitingdeterioration, it is necessary to recoat the concrete periodically. Theoperation of the sewerage system or the like has to be stopped for along time each time the concrete is coated.

Still further, a method in which concrete having excellent acidresistance and sulfate resistance is obtained by using slag cement orthe like having a high percentage content of sulfate is also known.However, the strength of this slag cement is poor and the deteriorationof the obtained concrete due to sulfuric acid cannot be completelyprevented.

DISCLOSURE OF THE INVENTION

An object of the present invention is to provide a deteriorationinhibitor for concrete or mortar which can effectively inhibit thedeterioration of concrete or mortar for a long time and to provide amethod of inhibiting the deterioration of concrete or mortar which usesthe inhibitor.

The present invention provides a deterioration inhibitor for concrete ormortar in which a phthalocyanine compound is an effective component.

Further, the present invention provides a method of inhibiting thedeterioration of concrete or mortar in which a phthalocyanine compoundis added to concrete or mortar.

Sulfur oxidizing bacteria exist in sewage or the like and cause thedeterioration of concrete or mortar. Several enzymes which relate to theoxidation-reduction of sulfur such as sulfideoxidase, sulfurdioxidase,or the like exist within a cell of the sulfur oxidizing bacteria, andsulfuric acid is generated due to the interaction of these enzymes(Koizumi, "Physiological Ecology and Biotechnology of Sulfur OxidizingBacteria", IRRIGATION WATER AND WASTE WATER, Vol. 31, page 307, 1989).Further, the sulfur oxidizing bacteria have the ecologicalcharacteristic in that a solid material such as a sulfur particle or thelike can be a substrate. As a result, a phthalocyanine compoundcontained in concrete or mortar can be easily introduced into a cell ofthe sulfur oxidizing bacteria. The phthalocyanine compound which hasbeen introduced into the cell of the sulfur oxidizing bacteria caninhibit and/or kill the sulfur oxidizing bacteria by inhibiting enzymereaction within the cell of the sulfur oxidizing bacteria.

Further, in the deterioration inhibitor of the present invention, thecomponent of the inhibitor is not eluted into sulfuric acid, unlike theabove-described deterioration inhibitors which contain a metal ormetallic oxide. Accordingly, a small amount of phthalocyanine compoundcan maintain the effect of inhibiting the deterioration of concrete overa long time. Furthermore, even if the above-described phthalocyaninecompound is a metal phthalocyanine or a metal phthalocyanine derivative,the amount of metal ion eluted by the sulfuric acid is extremely small.Thus, water is not polluted.

Moreover, compared to the aforementioned metal or metallic oxide, thephthalocyanine compound is easily dispersed within a polymeric componentincluded in a blending agent for concrete or mortar. Consequently, thephthalocyanine compound does not aggregate and precipitate in theblending agent, and a concrete or mortar in which a phthalocyaninecompound is dispersed uniformly can be prepared. As a result, the effectof preventing deterioration can be manifested throughout the entireconcrete or mortar.

BEST MODE FOR CARRYING OUT THE INVENTION

In the present invention, a phthalocyanine compound is a compound whichhas a phthalocyanine skeleton. More specifically, the phthalocyaninecompound is a metal phthalocyanine, a metal-free phthalocyanine, andderivatives thereof.

The metal phthalocyanine used in the present invention is a compound inwhich a metallic atom is coordinated at a phthalocyanine skeleton whichdoes not have a substituent. The metal phthalocyanine derivative is acompound which has a substituted atom other than a hydrogen atom or asubstituent bonded to a benzene ring within a metal phthalocyaninemolecule.

Further, the metal-free phthalocyanine used in the present invention isphthalocyanine (H₂ Pc) in which two hydrogen atoms are coordinated atthe center of the phthalocyanine skeleton. The metal-free phthalocyaninederivative is a compound which has a substituted atom other than ahydrogen atom or a substituent bonded to a benzene ring within ametal-free phthalocyanine molecule.

In the present invention, a phthalocyanine compound which is not solublein water is preferably used.

Concrete examples of the substituted atom other than a hydrogen atom orthe substituent in the metal phthalocyanine derivative and themetal-free phthalocyanine derivative include: halogen atoms such asfluorine, chlorine, bromine, and iodine; substituted or non-substitutedalkyl groups such as methyl group, ethyl group, propyl group, butylgroup, sec-butyl group, tert-butyl group, pentyl group, hexyl group,heptyl group, octyl group, stearyl group, trichloromethyl group,trifluoromethyl group, cyclopropyl group, cyclohexyl group,1,3-cyclohexadienyl group, 2-cyclopentene-1-yl group, and2,4-cyclopentadiene-1-ylidenyl group; substituted or non-substitutedalkoxy groups such as methoxy group, ethoxy group, propoxy group,n-butoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group,hexyloxy group, stearyloxy group, and trifluoromethoxy group;substituted or non-substituted thioalkoxy groups such as methylthiogroup, ethylthio group, propylthio group, butylthio group, sec-butylthiogroup, tert-butylthio group, pentylthio group, hexylthio group,heptylthio group, and octylthio group; nitro group; cyano group;carbonyl group; carboxyl group; ester group; hydroxyl group; sulfonicgroup; vinyl group; amino groups having at least one alkyl substituentsuch as methylamino group, dimethylamino group, ethylamino group,diethylamino group, dipropylamino group, and dibutylamino group; aminogroups having at least one carbocyclic aromatic substituent such asdiphenylamino group and ditolylamino group; amino groups having one ortwo of other substituents such as bis(acetooxymethyl)amino group,bis(acetooxyethyl)amino group, bis(acetooxypropyl)amino group,bis(acetooxybutyl)amino group, and dibenzylamino group; substituted ornon-substituted aryloxy groups such as phenoxy group,p-tert-butylphenoxy group, and 3-fluorophenoxy group; substituted ornon-substituted arylthio groups such as phenylthio group and3-fluorophenylthio group; substituted or non-substituted aromatic ringgroups such as phenyl group, biphenyl group, triphenyl group,tetraphenyl group, 3-nitrophenyl group, 4-methylthiophenyl group,3,5-dicyanophenyl group, o-, m-, and p-tolyl group, xylyl group, o-, m-,and p-cumenyl group, mesityl group, pentalenyl group, indenyl group,naphthyl group, azulenyl group, heptalenyl group, acenaphthylenyl group,phenalenyl group, fluolenyl group, antholyl group, anthraquinonyl group,3-methylantholyl group, phenantholyl group, triphenylene group, pyrenylgroup, chrysenyl group, 2-ethyl-1-chrysenyl group, picenyl group,perylenyl group, 6-chloroperylenyl group, pentaphenyl group, pentasenylgroup, tetraphenylene group, hexaphenyl group, hexasenyl group,rubisenyl group, coronenyl group, trinaphthylenyl group, heptaphenylgroup, heptasenyl group, pyrantrenyl group, and obalenyl group.

It is preferable that the metallic atom in the metal phthalocyanine andthe metal phthalocyanine derivative is at least one of iron, cobalt,nickel, palladium, tin, platinum, chromium, manganese, copper, zinc,lead, and rare earth elements. Rare earth elements include scandium,yttrium, lanthanum, cerium, praseodymium, neodymium, promethium,samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium,thulium, ytterbium, and lutetium.

In the present invention, it is more preferable that the phthalocyaninecompound is one of iron phthalocyanine, cobalt phthalocyanine, nickelphthalocyanine, tin phthalocyanine, metal-free phthalocyanine, and is aderivative in which one to eight hydrogen atom(s) in the benzene ring ofthese phthalocyanine molecules is substituted by a halogen atom, analkyl group having 1 to 6 carbon atoms, a nitro group, a cyano group, ahydroxyl group, or a sulfonic group.

One of the phthalocyanine compounds may be used, or alternatively, twoor more of the phthalocyanine compounds may be used in combination.

In the present invention, it is preferable that the phthalocyaninecompound is finely powdered so as to be mixed easily and uniformly withthe concrete or mortar. Further, the average particle diameter of thefine powder of the phthalocyanine compound is preferably 0.001 μm to 1mm and more preferably 0.01 μm to 0.1 mm.

In addition to the phthalocyanine compound, the deterioration inhibitorfor concrete or mortar of the present invention can contain a knownblending agent for concrete or mortar. Such blending agent may be, forexample, an AE agent/water reducing agent or a high-performance AE waterreducing agent which are used for improving the workability such asfluidity or the like, or an agent for increasing viscosity which is usedfor preventing the separation of materials.

The AE agent, water reducing agent and the high-performance AE waterreducing agent may be a high polymer such as naphthalenes,polycarboxylic acids, melamines, aminosulfonic acids, or the like.Further, the agent for increasing viscosity may be a polysaccharide suchas starch, guar gum, methylcellulose, carboxymethylcellulose, xanthangum, curdlan, or the like or derivatives thereof, or a synthetic highpolymer such as polyacrylamide, sodium polyacrylate, polyvinyl alcohol,or the like.

When the deterioration inhibitor for concrete or mortar of the presentinvention includes a blending agent, the amount of the phthalocyaninecompound added to the blending agent is based on the amount of theblending agent added to the concrete or mortar. The added amount of thephthalocyanine compound is preferably 5 to 500 parts by weight, morepreferably 10 to 100 parts by weight, based on 100 parts by weight ofthe blending agent.

When the deterioration inhibitor for concrete or mortar of the presentinvention includes a blending agent, it is preferable that thephthalocyanine compound is dispersed in the blending agent. In order todisperse the phthalocyanine compound in the blending agent, varioustypes of known grinders or dispersers can be used. More specifically, athree-roll mill or a two-roll mill which disperses the compound byshearing stress; a ball mill, an attriter, a sand mill, a cobol mill, abasket mill, an oscillating mill, or a paint conditioner which dispersesthe compound by impact force due to the collision with media such asglass beads, zirconia beads, an agate ball, or the like; a disperser, ahomogenizer, or a creamix (R) which disperses the compound by rotationalblades which generate shearing force, cavitation, collision force,potential core, or the like can be used. Further, a kneader, anextruder, a jet mill, an ultrasonic disperser, or the like can be used.

In the deterioration inhibitor for concrete or mortar of the presentinvention, the amount of the phthalocyanine compound added is preferably0.001 to 30 parts by weight, more preferably 0.01 to 5 parts by weight,based on 100 parts by weight of the cement component in the concrete ormortar. When the added amount of the phthalocyanine compound is lessthan 0.001 parts by weight, it is difficult to sustain the effect ofinhibiting and/or killing sulfur oxidizing bacteria over a long time. Onthe other hand, when the added amount of the phthalocyanine compoundexceeds 30 parts by weight, it is not preferable since improvement ofthe sulfur oxidizing bacteria inhibiting and/or killing effect cannot beexpected any more and the cost of implementing the method of inhibitingthe deterioration of concrete is high. Further, the strength of theconcrete or mortar is greatly reduced.

EXAMPLES

The present invention will be described in detail hereinafter inaccordance with Examples and Comparative Examples. However, the presentinvention is not limited to these.

Examples 1 to 22

2.5 parts by weight of each of the phthalocyanine compounds shown inTable 1 and having an average particle diameter of 1.0 μm was added to amortar component formed of 100 parts by weight of cement, 200 parts byweight of sand, and 50 parts by weight of water and was kneaded fullywith the mortar component by using a mortar mixer. The mixture wasplaced in a mold and molded, and thereafter, was cured for 28 days (24hours in a moist box and 27 days in water). A mortar specimen wasthereby obtained.

Examples 23 to 44

3.0 parts by weight of each of the phthalocyanine compounds shown inTable 1 and having an average particle diameter of 1.0 μm was added to aconcrete component formed of 120 parts by weight of cement and 80 partsby weight of water and was kneaded fully with the concrete component byusing a concrete mixer. The mixture was placed in a mold and molded, andthereafter, was cured for 28 days (24 hours in a moist box and 27 daysin water). A concrete specimen was thereby obtained.

Examples 45 to 58

0.1 parts by weight of each of the phthalocyanine compounds shown inTable 1 and having an average particle diameter of 1.0 μm was added to amortar component formed of 100 parts by weight of cement, 200 parts byweight of sand, and 50 parts by weight of water and was kneaded fullywith the concrete component by using a mortar mixer. The mixture wasplaced in a mold and molded, and thereafter, was cured for 28 days (24hours in a moist box and 27 days in water). A mortar specimen wasthereby obtained.

                  TABLE 1                                                         ______________________________________                                                   Phthalocyanine         Phthalocyanine                                Example No. compound Example No. compound                                   ______________________________________                                        1, 23      CrPc        12, 34, 48 H.sub.2 Pc                                    2, 24 MnPc 13, 35, 49 NiPc--Cl.sub.4                                          3, 25 FePc 14, 36, 50 NiPc-(t-Bu).sub.4                                       4, 26, 45 CoPc 15, 37, 51 NiPc--(CN).sub.4                                    5, 27, 46 NiPc 16, 38, 52 NiPc--(NO.sub.2).sub.4                              6, 28 CuPc 17, 39, 53 NiPc--(CN).sub.8                                        7, 29 ZnPc 18, 40, 54 H.sub.2 Pc--Cl.sub.4                                    8, 30 PdPc 19, 41, 55 H.sub.2 Pc-(t-Bu).sub.4                                 9, 31, 47 SnPc 20, 42, 56 H.sub.2 Pc--(CN).sub.4                              10, 32 PtPc 21, 43, 57 H.sub.2 Pc--(NO.sub.2).sub.4                           11, 33 PbPc 22, 44, 58 H.sub.2 Pc--(CN).sub.8                               ______________________________________                                    

In Table 1, CrPc, MnPc, FePc, CoPc, NiPc, CuPc, ZnPc, PdPc, SnPc, PtPc,and PbPc denote metal phthalocyanines whose metal atoms are respectivelychromium, manganese, iron, cobalt, nickel, copper, zinc, palladium, tin,platinum, and lead, and H₂ Pc denotes a metal-free phthalocyanine.Further, Cl, t-Bu, CN, and NO₂ denote substituent atoms or substituents,i.e., chlorine atom, tert-butyl group, cyano group, and nitro group,respectively.

Comparative Example 1

A mortar specimen was obtained using a method similar to that of Example1 except that a phthalocyanine compound was not added to the mortarspecimen.

Comparative Example 2

A mortar specimen was obtained using a method similar to that of Example1 except that an organic nitrogen sulfur antibacterial agent ("FINE SANDA-3" manufactured by Tokyo Fine Chemical Co.) was added to the mortarspecimen instead of a phthalocyanine compound.

Comparative Example 3

A concrete specimen was obtained using a method similar to that ofExample 23 except that a phthalocyanine compound was not added to theconcrete specimen.

Comparative Example 4

A concrete specimen was obtained using a method similar to that ofExample 23 except that an organic nitrogen sulfur antibacterial agent("FINE SAND A-3" manufactured by Tokyo Fine Chemical Co.) was added tothe concrete specimen instead of a phthalocyanine compound.

The specimens obtained in the Examples and Comparative Examples wereexposed to sludge on the walls of a sludge facility of a sewage disposalplant for nine months. The extent of adhesion of sulfur oxidizingbacteria and the extent of plastering of the specimen were evaluated asfollows. The results are shown in Tables 2 to 4. (Extent of Adhesion ofSulfur Oxidizing Bacteria)

The surface of the specimen was washed by 50 ml of sterilized water(sterilized for 20 minutes in an autoclave) with a toothbrush. Thewashing solution was treated by ultrasonication, and thereafter, wasdiluted. The solution was cultured at a temperature of 30° C. for 11days by using an ONM solid medium to which yeast extract was added andwhich was set by gellan gum (Imai, Watami, Katagiri, "Growing Conditionsof Bacteria by Biochemical Research (Second Report) on Sulfur OxidizingBacteria", FERMENTATION INDUSTRY, Vol. 42, page 762, 1964). Then, thenumber of growth colonies was counted. The number of sulfur oxidizingbacteria per 1 ml of washing solution (cell/ml) was obtained from thisvalue, and the extent of adhesion of the sulfur oxidizing bacteria wasevaluated on the basis of the evaluation criteria described below.

Evaluation criteria for extent of adhesion of sulfur oxidizing bacteria

Evaluation 1: 10⁶ cell/ml or more

Evaluation 2: 10⁴ to 10⁶ cell/ml

Evaluation 3: 10² to 10⁴ cell/ml

Evaluation 4: less than 10² cell/ml

Evaluation 5: no adhesion was detected

Extent of Plastering

10 gram of the surface of the specimen was sampled and the amount ofcalcium sulfate was measured using an X-ray diffractometer. The ratio(%) of calcium sulfate, which is a corrosion product of calcium bysulfate, to calcium in the surface of the specimen was obtained fromthis value, and the extent of plastering of the specimen was evaluatedon the basis of the evaluation criteria described below.

Evaluation criteria for extent of plastering of the specimen

Evaluation 1: 80% or more

Evaluation 2: 50 to 80%

Evaluation 3: 30 to 50%

Evaluation 4: 1 to 30%

Evaluation 5: no plastering was detected

                  TABLE 2                                                         ______________________________________                                                 Extent of Adhesion of                                                  Sulfur Oxidizing                                                              Bacteria Extent of Plastering                                               ______________________________________                                        Example 1  Evaluation 5  Evaluation 5                                           Example 2 Evaluation 4 Evaluation 4                                           Example 3 Evaluation 4 Evaluation 4                                           Example 4 Evaluation 4 Evaluation 5                                           Example 5 Evaluation 5 Evaluation 5                                           Example 6 Evaluation 4 Evaluation 4                                           Example 7 Evaluation 4 Evaluation 5                                           Example 8 Evaluation 4 Evaluation 5                                           Example 9 Evaluation 5 Evaluation 5                                           Example 10 Evaluation 4 Evaluation 5                                          Example 11 Evaluation 5 Evaluation 5                                          Example 12 Evaluation 4 Evaluation 4                                          Example 13 Evaluation 5 Evaluation 5                                          Example 14 Evaluation 4 Evaluation 5                                          Example 15 Evaluation 5 Evaluation 5                                          Example 16 Evaluation 4 Evaluation 5                                          Example 17 Evaluation 5 Evaluation 5                                          Example 18 Evaluation 5 Evaluation 5                                          Example 19 Evaluation 4 Evaluation 5                                          Example 20 Evaluation 5 Evaluation 5                                          Example 21 Evaluation 4 Evaluation 5                                        ______________________________________                                    

                  TABLE 3                                                         ______________________________________                                                 Extent of Adhesion of                                                  Sulfur Oxidizing                                                              Bacteria Extent of Plastering                                               ______________________________________                                        Example 22 Evaluation 5  Evaluation 5                                           Example 23 Evaluation 5 Evaluation 5                                          Example 24 Evaluation 4 Evaluation 5                                          Example 25 Evaluation 4 Evaluation 5                                          Example 26 Evaluation 5 Evaluation 5                                          Example 27 Evaluation 5 Evaluation 5                                          Example 28 Evaluation 4 Evaluation 4                                          Example 29 Evaluation 5 Evaluation 5                                          Example 30 Evaluation 5 Evaluation 5                                          Example 31 Evaluation 5 Evaluation 5                                          Example 32 Evaluation 5 Evaluation 5                                          Example 33 Evaluation 5 Evaluation 5                                          Example 34 Evaluation 4 Evaluation 4                                          Example 35 Evaluation 4 Evaluation 5                                          Example 36 Evaluation 5 Evaluation 5                                          Example 37 Evaluation 5 Evaluation 5                                          Example 38 Evaluation 5 Evaluation 5                                          Example 39 Evaluation 5 Evaluation 5                                          Example 40 Evaluation 4 Evaluation 5                                          Example 41 Evaluation 4 Evaluation 4                                          Example 42 Evaluation 5 Evaluation 5                                          Example 43 Evaluation 4 Evaluation 4                                        ______________________________________                                    

                  TABLE 4                                                         ______________________________________                                                 Extent of Adhesion of                                                  Sulfur Oxidizing                                                              Bacteria Extent of Plastering                                               ______________________________________                                        Example 44 Evaluation 5  Evaluation 5                                           Example 45 Evaluation 4 Evaluation 5                                          Example 46 Evaluation 5 Evaluation 5                                          Example 47 Evaluation 5 Evaluation 5                                          Example 48 Evaluation 4 Evaluation 4                                          Example 49 Evaluation 5 Evaluation 5                                          Example 50 Evaluation 4 Evaluation 5                                          Example 51 Evaluation 5 Evaluation 5                                          Example 52 Evaluation 4 Evaluation 5                                          Example 53 Evaluation 5 Evaluation 5                                          Example 54 Evaluation 5 Evaluation 5                                          Example 55 Evaluation 4 Evaluation 5                                          Example 56 Evaluation 5 Evaluation 5                                          Example 57 Evaluation 4 Evaluation 5                                          Example 58 Evaluation 5 Evaluation 5                                          Comparative Evaluation 1 Evaluation 1                                         Example 1                                                                     Comparative Evaluation 1 Evaluation 1                                         Example 2                                                                     Comparative Evaluation 1 Evaluation 1                                         Example 3                                                                     Comparative Evaluation 1 Evaluation 2                                         Example 4                                                                   ______________________________________                                    

In the specimen which contains the phthalocyanine compound of thepresent invention, the evaluations of the extent of adhesion of thesulfur oxidizing bacteria and the extent of plastering are 4 and 5.However, in the specimen which does not contain the phthalocyaninecompound and the specimen which contains the organic nitrogen sulfurantibacterial agent instead of the phthalocyanine compound, the adhesionof sulfur oxidizing bacteria to the specimen is marked, the surface ofthe specimen is plastered, and the specimen is deteriorated.

As a result, it is found that the phthalocyanine compound of the presentinvention is effective against the deterioration of concrete or mortarby sulfur oxidizing bacteria.

Industrial Applicability

In the deterioration inhibitor for concrete or mortar and the method ofinhibiting the deterioration of concrete or mortar of the presentinvention, water is not polluted and a small amount of inhibitor canprevent the deterioration of concrete or mortar due to sulfur oxidizingbacteria for a long time. Therefore, the inhibitor and the method can beused for wide applications such as various structures in which concreteor mortar is used.

What is claimed is:
 1. A deterioration inhibitor for concrete or mortarcomprising a phthalocyanine compound and a blending agent for concreteor mortar, said blending agent selected from the group consisting of anair entraining agent, a water reducing agent, and a viscosity increasingagent, said phthalocyanine compound being present in an amount of 5 to500 parts by weight based on 100 parts by weight of said blending agent.2. A deterioration inhibitor for concrete or mortar according to claim1, wherein the phthalocyanine compound is a metal phthalocyanine and/ora metal phthalocyanine derivative.
 3. A deterioration inhibitor forconcrete or mortar according to claim 2, wherein the metal atom of themetal phthalocyanine and/or metal phthalocyanine derivative is selectedfrom the group consisting of iron, cobalt, nickel, palladium, tin andplatinum.
 4. A deterioration inhibitor for concrete or mortar accordingto claim 2, wherein the metal atom of the metal phthalocyanine and/ormetal phthalocyanine derivative is selected from the group consisting ofmanganese, copper, zinc and lead.
 5. A deterioration inhibitor forconcrete or mortar according to claim 2, wherein the metal atom of themetal phthalocyanine and/or metal phthalocyanine derivative is a rareearth element.
 6. A deterioration inhibitor for concrete or mortaraccording to claim 1, wherein the phthalocyanine compound is ametal-free phthalocyanine and/or a metal-free phthalocyanine derivative.7. A deterioration inhibitor for concrete or mortar according to claim2, wherein the metal phthalocyanine and/or metal phthalocyaninederivative contains a moiety selected from the group consisting ofchloro, t-butyl, cyano, and nitro.
 8. A method of inhibiting thedeterioration of concrete or mortar comprising adding to concrete ormortar a deterioration-inhibiting effective amount of a phthalocyaninecompound, said phthalocyanine compound being selected from the group ofconsisting of a metal phthalocyanine, a metal phthalocyanine derivative,a metal-free phthalocyanine and a metal-free phthalocyanine derivative,the metal atom of said metal phthalocyanine and/or said metalphthalocyanine derivative being selected from the group consisting ofchromium, manganese, copper, zinc, lead and a rare earth element.
 9. Amethod of inhibiting the deterioration of concrete or mortar accordingto claim 8, wherein said phthalocyanine compound is present in an amountof 0.001 to 30 parts by weight per 100 parts by weight of a cementcomponent contained in the concrete or mortar.
 10. A method ofinhibiting the deterioration of concrete or mortar according to claim 8,further comprising adding a blending agent for concrete or mortar to theconcrete or mortar, said blending agent selected from the groupconsisting of an air entraining agent, a water reducing agent, and aviscosity increasing agent, said phthalocyanine compound being presentin an amount of 5 to 500 parts by weight based on 100 parts by weight ofsaid blending agent.
 11. A method of inhibiting the growth of sulfuroxidizing bacteria on a surface of a concrete or mortar comprisingadding to concrete or mortar a phthalocyanine compound in an amount of0.001 to 30 parts by weight based on 100 parts by weight of a cementcomponent contained in said concrete or mortar, said phthalocyaninecompound being selected from the group consisting of a metalphthalocyanine and a metal phthalocyanine derivative whose metal atom isselected from the group consisting of iron, cobalt, nickel, palladium,tin and platinum.
 12. A method inhibiting the deterioration of concreteor mortar according to claim 11, further comprising adding a blendingagent for concrete or mortar to the concrete or mortar, said blendingagent selected from the group consisting of an air entraining agent, awater reducing agent, and a viscosity increasing agent, saidphthalocyanine compound being present in an amount of 5 to 500 parts byweight based on 100 parts by weight of said blending agent.